CN106946734B - A kind of method of high-selectivity oxidation benzylamine green syt N- benzylidenebutyramide - Google Patents
A kind of method of high-selectivity oxidation benzylamine green syt N- benzylidenebutyramide Download PDFInfo
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- CN106946734B CN106946734B CN201710090604.3A CN201710090604A CN106946734B CN 106946734 B CN106946734 B CN 106946734B CN 201710090604 A CN201710090604 A CN 201710090604A CN 106946734 B CN106946734 B CN 106946734B
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- tungstate
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- benzylidenebutyramide
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- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- WYSRMZBCJRNZKB-UHFFFAOYSA-N N-benzylidenebutanamide Chemical compound C(C1=CC=CC=C1)=NC(CCC)=O WYSRMZBCJRNZKB-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 16
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000243 solution Substances 0.000 claims abstract description 36
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 35
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 30
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 27
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 230000008025 crystallization Effects 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000011941 photocatalyst Substances 0.000 claims abstract description 22
- 238000005286 illumination Methods 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000010189 synthetic method Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 16
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 12
- 229910001882 dioxygen Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- MRZDCFAGABOHQQ-UHFFFAOYSA-N chromium(3+);dioxido(dioxo)tungsten Chemical compound [Cr+3].[Cr+3].[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O MRZDCFAGABOHQQ-UHFFFAOYSA-N 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000004445 quantitative analysis Methods 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000004451 qualitative analysis Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 208000019155 Radiation injury Diseases 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000003782 beta lactam antibiotic agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229940035637 spectrum-4 Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002132 β-lactam antibiotic Substances 0.000 description 1
- 229940124586 β-lactam antibiotics Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of methods of high-selectivity oxidation benzylamine green syt N- benzylidenebutyramide.This method comprises: cadmium tungstate, bismuth tungstate is taken to be dissolved in alcoholic solution, it is uniformly mixed；By mixed solution crystallization, cadmium tungstate-bismuth tungstate composite photocatalyst is made through cooling, filtering, separation, drying and other steps after；It takes cadmium tungstate-bismuth tungstate composite photocatalyst to be dispersed in benzylamine, is passed through oxygen, illumination is to get N- benzylidenebutyramide.The present invention can improve the conversion ratio of benzylamine by controlling the ratio of catalyst, and obtained N- benzylidenebutyramide is selectively greater than 99%.The present invention has the characteristics that green, solvent-free, efficient, low energy consumption, and synthesis technology is simple.
Description
[technical field]
The present invention relates to photochemical catalytic oxidation fields, and in particular to a kind of high-selectivity oxidation benzylamine green syt N- benzyl alkene fourth
The method of amine.
[background technique]
Imines is intermediate important in organic synthesis, has important application in biomedicine field.Due to electrophilic
Property double bond, imines can occur important to react with other reagents.N- benzylidenebutyramide can be used for synthesizing as one kind has bioactivity
Natural products and drug candidate important chemical industry product, addition reaction can occurs in it with ester, acyl chlorides, ketenes etc., and to generate β-interior
Amide, and the extensive use of beta-lactam antibiotic makes the oxidative synthesis N- benzylidenebutyramide of benzylamine be of great significance.Tradition
Synthetic method formed with condensation using primary amine.The method needs thermal dehydration device, operates more troublesome and very much
Raw material is not easy to prepare.In recent years, oxidation benzylamine preparation N- benzylidenebutyramide becomes a kind of effective ways, especially under catalytic condition
The green oxidation synthetic method carried out with oxygen, hydrogen peroxide etc. receives significant attention.
It mainly includes the dehydrogenation of metal catalytic, microwave method, HgO-I that oxidizing process, which prepares the technique of N- benzylidenebutyramide, at present2Oxygen
Change etc..But existing method for oxidation remains certain defects: higher reaction temperature, longer reaction time, reaction
Or a large amount of organic solvent is used in post-processing.In recent years, photocatalytic oxidation using solar energy as energy source, with molecule
Oxygen realizes organic matter selective oxidation process, by the concern of researchers as oxidant under room temperature or lower temperature.
So far, the heterogeneous catalyst for benzylamine oxidation mainly has TiO2With with TiO2Based on modified light catalyst, WS2、
Au/SrTiO3、Nb2O5And the novel photocatalyst g-C developed recently3N4.But there are photocatalytic activities for these photochemical catalysts
The disadvantages of low, visible light-responded weak.Therefore, it develops a kind of efficiency light and urges agent to realize high-selectivity oxidation benzylamine green syt N-
Benzylidenebutyramide is extremely important and urgent.
Bismuth tungstate (Bi2WO6) it is a kind of cheap, stable and nontoxic pigment, forbidden bandwidth is about 2.7eV, is had relatively strong
Visible light absorption capacity, be applied to the fields such as photocatalysis organic matter degradation, photocatalytic water and organic synthesis.Cadmium tungstate
(CdWO4) belonging to monoclinic system crystal, forbidden bandwidth is about 2.7eV, and it is with the high and low radiation injury of refractive index, hair
Luminous intensity is greatly and the advantages that excellent scintillation properties.
The advantages of by using bismuth tungstate and cadmium tungstate, can develop with visible light-responded, mild oxidation ability, compared with
The catalysis material of the advantages that high visible light catalytic activity, caused industry future realize N- benzylidenebutyramide photocatalytic synthesis at it is strong
Strong concern.
[summary of the invention]
The purpose of the present invention is a kind of method of highly selective catalysis oxidation benzylamine synthesis N- benzylidenebutyramide, this method is high
It is effect, low energy consumption, pollution-free.
It is as follows that the present invention prepares the step of effective catalyst:
It takes cadmium tungstate, bismuth tungstate to be dissolved in alcoholic solution, is uniformly mixed；
It is multiple through cooling, filtering, separation, the obtained cadmium tungstate-bismuth tungstate of drying and other steps after by mixed solution crystallization
Light combination catalyst；
It takes cadmium tungstate-bismuth tungstate composite photocatalyst to be dispersed in benzylamine, is passed through oxygen, illumination is to get N- benzylidenebutyramide.
The cadmium tungstate, bismuth tungstate can both be purchased from it is commercially available, also can now-making-now-using.
Preferably, the cadmium tungstate, bismuth tungstate mixed solution, wherein the concentration of tungstate radicle is 1~50mmol/l.
Preferably, the crystallization temperature is 100~200 DEG C, and crystallization time is 10~48h.
Preferably, the alcoholic solution is ethyl alcohol, ethylene glycol or three ethanol solutions.
Preferably, based on the gross mass of reactant, the speed for being passed through oxygen is 20~400mL/min/g.
Preferably, the light irradiation time be 1~for 24 hours.
Preferably, the light source of the illumination is xenon lamp, and filters out light of the wavelength less than 400 nanometers.
Preferably, the molar ratio in the cadmium tungstate-bismuth tungstate composite photocatalyst between cadmium tungstate and bismuth tungstate is 1:
[1~10].
The present invention can prepare CdWO by changing the molar ratio of cadmium and bismuth4-Bi2WO6Composite photo-catalyst, for height
Selective catalytic oxidation benzylamine synthesizes N- benzylidenebutyramide, has the characteristics that efficient, green, energy consumption is small, corrosion-free equipment, benzylamine turns
The selectivity that rate is greater than 10%, N- benzylidenebutyramide is greater than 99%.
[specific embodiment]
Below with reference to the embodiment of the present invention, the present invention will be further described；In the following example, cadmium tungstate, bismuth tungstate are equal
It for now-making-now-using, directlys adopt commercially available cadmium tungstate, bismuth tungstate and following embodiments and has same effect, and not to the present invention
Technical solution bring substantial effect.
Embodiment 1
The present invention prepares light with the different mol ratio of chromium tungstate in cadmium tungstate-bismuth tungstate composite photocatalyst, bismuth tungstate and urges
Agent:
The preparation of cadmium tungstate: 1.234g cadmium nitrate is taken to be dissolved in 40ml deionized water and mix with 0.240g ethylenediamine solution
It closes, stirs evenly to form solution A；Sodium tungstate is dissolved in 40ml water and obtains solution B；10min is mixed in AB, obtains solution
C；Then by resulting solution C 180 DEG C crystallization 20 hours.Crystallization liquid is separated through cold filtration, be washed with deionized three times,
Dehydrated alcohol washed once, and can obtain cadmium tungstate within dry 6 hours in 80 DEG C；
The preparation of composite material: it takes 0.041g sodium tungstate to be dissolved in 10ml ethylene glycol solution, stirs evenly to form solution D；
It takes 0.121g bismuth nitrate to be dissolved in 10ml ethylene glycol solution, stirs evenly to form solution E；10min is mixed in DE, is obtained molten
Liquid F；Then 0.036g cadmium tungstate is added in F solution, and 60ml ethyl alcohol is added and forms solution in wherein mixing 10min
G, by resulting solution G 160 DEG C crystallization 24 hours.Crystallization liquid is separated through cold filtration, be washed with deionized three times, it is anhydrous
Ethanol washing is primary, and 80 DEG C of dryings can obtain composite photo-catalyst in 6 hours.
Using under visible light, molecular oxygen as oxidizer catalytic oxidation benzylamine preparation N- benzylamine butylene as model reaction investigation
The photocatalytic activity of prepared catalyst:
Composite photocatalyst material prepared by taking 50 milligrams, is then added 10mmol benzylamine, and control oxygen gas flow rate is 60mL/
Then min/g opens light source (300 watts of xenon lamp is added optical filter and filters light of the wavelength less than 400 nanometers) illumination 5h, simultaneously
Opening condensation water management reacting liquid temperature is room temperature.Illumination samples after a certain period of time, is centrifugated out catalyst, then uses gas
Phase chromatography-mass spectroscopy is used in conjunction instrument and carries out qualitative analysis to product, using gas chromatograph (GC2010, the detection of hydrogen flameionization device
Device, Shimadzu Corporation produce) quantitative analysis is carried out to product, using biphenyl as internal standard compound when quantitative analysis, benzylamine catalysis oxidation is obtained
The product arrived is N- benzylidenebutyramide.
Embodiment 2~5
Cadmium tungstate, bismuth tungstate composite photocatalyst to different mol ratio, operating procedure is similar with embodiment 1, only changes
The amount that the sodium tungstate and bismuth nitrate of change composite material are added, remaining condition is constant, and is Cat 2, Cat 3, Cat sample number into spectrum
4,Cat 5.The composite catalyst condition and reaction result of Examples 1 to 5 preparation are shown in Table 1.
The composite photo-catalyst preparation condition and reaction result of 1 different mol ratio of table
Find that cadmium tungstate-bismuth tungstate of 4 this ratio of Cat makes benzylamine conversion ratio be 38.7%, N- benzyl alkene fourth by table 1
The selectivity of amine is greater than 99%, has optimal photocatalysis effect.
Embodiment 6~10
4 step of embodiment for being 1:7.5 according to the optimal molar ratio of chromium tungstate, bismuth tungstate effect in reaction mixture,
Remaining condition is constant, changes the crystallization temperature of composite photo-catalyst preparation, 100 DEG C, 120 DEG C, 140 DEG C, 180 DEG C, 200 are respectively adopted
For 24 hours, it is T 1, T 2, T 3, T 4, T 5 that its sample, which is compiled, respectively for DEG C crystallization, remaining operating procedure is similar to Example 4.Implement
Composite catalyst condition and reaction result prepared by example 6~10 is shown in Table 2.
2 chromium tungstate of table, bismuth tungstate molar ratio be 1:7.5 difference crystallization temperature condition and reaction result
Different benzylamine conversion ratios is obtained under different crystallization temperatures by the discovery of table 2, wherein the temperature and 4 phase of embodiment
160 degree of comparison discovery is optimal crystallization temperature.
Embodiment 11~13
4 step of embodiment for being 1:7.5 according to the optimal molar ratio of chromium tungstate, bismuth tungstate effect in reaction mixture, changes
Become the crystallization time of composite photo-catalyst preparation, respectively 12h, 36h, 48h.And its sample compile be H1, H 2, H3, remaining
Condition is constant.Reaction condition is same as Example 4, the composite photo-catalyst preparation condition of 11~13 different mol ratio of embodiment and
Reaction result is shown in Table 3.
The composite photo-catalyst preparation condition and reaction result of 3 different mol ratio of table
Different benzylamine conversion ratios is obtained under different crystallization times by the discovery of table 3, wherein the temperature and 4 phase of embodiment
Comparison discovery is optimal crystallization time for 24 hours.
Embodiment 14~18
Molar ratio according to chromium tungstate, bismuth tungstate is that 1:7.5 composite material optimal effectiveness is catalyst, probes into it and reacts item
Influence of the change of part to its photochemical catalytic oxidation.For controlling the different flow velocity of oxygen, be respectively adopted 20mL/min/g,
The oxygen gas flow rate of 120mL/min/g, 240mL/min/g, 360mL/min/g and 400mL/min/g, be denoted as accordingly V1, V2,
V3, V4, V5, remaining reaction conditioned response condition is same as Example 4, obtains corresponding reaction result and is shown in Table 4.
4 chromium tungstate of table, bismuth tungstate molar ratio be 1:7.5 under the conditions of different oxygen gas flow rates and reaction result
The reaction result of different oxygen gas flow rates under the conditions of being 1:7.5 by the molar ratio of 4 chromium tungstate of table, bismuth tungstate, discovery should
Catalyst is best in the reaction effect that flow velocity is 60mL/min/g.
Embodiment 19~22
Molar ratio according to chromium tungstate, bismuth tungstate is that 1:7.5 composite material optimal effectiveness is catalyst, when probing into its illumination
Between influence of the change to its photochemical catalytic oxidation.Be respectively adopted light application time be 1h, 10h, 15h, 24, be denoted as respectively L1, L2,
L3, L4.Remaining reaction conditioned response condition is same as Example 4, obtains corresponding reaction result and is shown in Table 5.
5 chromium tungstate of table, bismuth tungstate molar ratio be 1:7.5 under the conditions of different light application times and reaction result
The reaction result of different light application times under the conditions of being 1:7.5 by the molar ratio of 5 chromium tungstate of table, bismuth tungstate, discovery should
Catalyst is being increased with the growth conversion ratio of time, but the rate in reaction 5h is most fast.The catalyst is finally obtained to exist
Light application time most preferably 5h.
Comparative example 1
The preparation method of cadmium tungstate: take 1.234g cadmium nitrate be dissolved in 40ml deionized water and with 0.240g ethylenediamine solution
Mixing, stirs evenly to form solution A；Sodium tungstate is dissolved in 40ml water and obtains solution B；10min is mixed in AB, is obtained molten
Liquid C；Then by resulting solution C 180 DEG C crystallization 20 hours.Crystallization liquid is separated through cold filtration, is washed with deionized three
Secondary, dehydrated alcohol washed once, and 80 DEG C of dryings can obtain cadmium tungstate in 6 hours.
Using under visible light, molecular oxygen as oxidizer catalytic oxidation benzylamine preparation N- benzylamine butylene as model reaction investigation
The photocatalytic activity of prepared catalyst: then 10mmol benzylamine, control is added in composite photocatalyst material prepared by taking 50 milligrams
Oxygen gas flow rate processed is 60mL/min/g, and then opening light source, (300 watts of xenon lamp is added optical filter and filters wavelength less than 400 nanometers
Light) illumination 5h, open simultaneously condensation water management reacting liquid temperature be room temperature.Illumination samples after a certain period of time, and centrifugation is isolated
Then catalyst uses gas chromatography-mass spectrum that instrument is used in conjunction and carries out qualitative analysis to product, using gas chromatograph (GC2010, hydrogen
Flame ion device detector, Shimadzu Corporation produce) quantitative analysis is carried out to product, using biphenyl as internal standard when quantitative analysis
Object.Benzylamine conversion ratio is that the selectivity of 2.3%, N- benzylidenebutyramide is greater than 99%.
Comparative example 2
The preparation method of bismuth tungstate: it takes 0.247g sodium tungstate to be dissolved in 10ml ethylene glycol solution, stirs evenly to form solution
A；It takes 0.679g bismuth nitrate to be dissolved in 10ml ethylene glycol solution, stirs evenly to form solution B；10min is mixed in AB, is obtained
Solution C；And 60ml ethyl alcohol is added and forms solution D stirring 10min in wherein stirring, then by resulting solution D in 160 DEG C of crystallization
24 hours.Crystallization liquid is separated through cold filtration, be washed with deionized three times, dehydrated alcohol washed once, 80 DEG C drying 6 hours
Composite photo-catalyst can be obtained.
Using under visible light, molecular oxygen as oxidizer catalytic oxidation benzylamine preparation N- benzylamine butylene as model reaction investigation
The photocatalytic activity of prepared catalyst: then 10mmol benzylamine, control is added in composite photocatalyst material prepared by taking 50 milligrams
Oxygen gas flow rate processed is 60mL/min/g, and then opening light source, (300 watts of xenon lamp is added optical filter and filters wavelength less than 400 nanometers
Light) illumination 5h, open simultaneously condensation water management reacting liquid temperature be room temperature.Illumination samples after a certain period of time, and centrifugation is isolated
Then catalyst uses gas chromatography-mass spectrum that instrument is used in conjunction and carries out qualitative analysis to product, using gas chromatograph (GC2010, hydrogen
Flame ion device detector, Shimadzu Corporation produce) quantitative analysis is carried out to product, using biphenyl as internal standard when quantitative analysis
Object.Benzylamine conversion ratio is that the selectivity of 12.2%, N- benzylidenebutyramide is greater than 99%.
Comparative example 3
It takes commercially available cadmium tungstate 0.036g and 0.523g bismuth tungstate is taken to be dissolved in 10ml ethylene glycol solution respectively, stir evenly
Form solution A；10min is mixed after to be dissolved and forms solution B；And 60ml ethyl alcohol is added and forms solution C in wherein stirring and stirs
Mix 10min, then by resulting solution C 160 DEG C crystallization 24 hours.Crystallization liquid is separated through cold filtration, is washed with deionized water
Wash three times, dehydrated alcohol washed once, 80 DEG C of dryings can obtain composite photo-catalyst in 6 hours.
Using under visible light, molecular oxygen as oxidizer catalytic oxidation benzylamine preparation N- benzylamine butylene as model reaction investigation
The photocatalytic activity of prepared catalyst: then 10mmol benzylamine, control is added in composite photocatalyst material prepared by taking 50 milligrams
Oxygen gas flow rate processed is 60mL/min/g, and then opening light source, (300 watts of xenon lamp is added optical filter and filters wavelength less than 400 nanometers
Light) illumination 5h, open simultaneously condensation water management reacting liquid temperature be room temperature.Illumination samples after a certain period of time, is centrifugated out
Then catalyst uses gas chromatography-mass spectrum that instrument is used in conjunction and carries out qualitative analysis to product, using gas chromatograph (GC2010, hydrogen
Flame ion device detector, Shimadzu Corporation produce) quantitative analysis is carried out to product, using biphenyl as internal standard when quantitative analysis
Object.Benzylamine conversion ratio is that the selectivity of 10.2%, N- benzylidenebutyramide is greater than 99%.
It can be seen that the photochemical catalyst photochemical catalytic oxidation benzyl that the method for the present invention is made compound from above-described embodiment and comparative example
Amine synthesizes N- benzylamine butylene at room temperature being capable of efficient, highly selective preparation N- benzylamine under visible light using molecular oxygen as oxidant
Butylene, which is more compared, has preferably activity with commercially available catalyst.
Claims (8)
1. a kind of method of high-selectivity oxidation benzylamine synthesis N- benzylidenebutyramide comprising the steps of:
It takes cadmium tungstate, bismuth tungstate to be dissolved in alcoholic solution, is uniformly mixed；
By mixed solution crystallization, cadmium tungstate-bismuth tungstate complex light is made through cooling, filtering, separation, drying and other steps after
Catalyst；
It takes cadmium tungstate-bismuth tungstate composite photocatalyst to be dispersed in benzylamine, is passed through oxygen, illumination is to get N- benzylidenebutyramide.
2. synthetic method according to claim 1, which is characterized in that the cadmium tungstate, bismuth tungstate mixed solution, wherein tungsten
The concentration of acid group is 1~50mmol/l.
3. synthetic method according to claim 1, which is characterized in that the crystallization temperature is 100~200 DEG C, when crystallization
Between be 10~48h.
4. synthetic method according to claim 1, which is characterized in that the alcoholic solution is ethyl alcohol, ethylene glycol or three ethyl alcohol
Solution.
5. synthetic method according to claim 1, which is characterized in that described to be passed through oxygen based on the gross mass of reactant
Speed be 20~400mL/min/g.
6. synthetic method according to claim 1, which is characterized in that the light irradiation time be 1~for 24 hours.
7. synthetic method according to claim 1, which is characterized in that the light source of the illumination is xenon lamp, and filters out wave
The long light less than 400 nanometers.
8. synthetic method according to claim 1, which is characterized in that in the cadmium tungstate-bismuth tungstate composite photocatalyst
Molar ratio between cadmium tungstate and bismuth tungstate is 1:[1~10].
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